- A ligand-free, powerful, and practical method for methoxylation of unactivated aryl bromides by use of the CuCl/HCOOMe/MeONa/MeOH system
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A ligand-free, powerful, and practical method for mono and polymethoxylation of unactivated aryl bromides has been developed; CuCl was used as catalyst, HCOOMe as cocatalyst, and methanolic MeONa as both nucleophile and solvent. This eco-friendly procedure is characterized by operational simplicity, inexpensive substrates (unactivated mono to polybromoarenes), full conversion, and direct recovery of pure MeOH.
- Guo, Ying,Ji, Si-Zhe,Chen, Cheng,Liu, Hong-Wei,Zhao, Jian-Hong,Zheng, Yu-Lin,Ji, Ya-Fei
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p. 8651 - 8664
(2015/03/05)
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- ANTIBACTERIAL AGENTS: ARYL MYXOPYRONIN DERIVATIVES
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The invention provides compounds of formula la, lb and Ic: [Formula Ia, Ib, and Ic] and salts thereof, wherein variables are as described in the specification, as well as compositions comprising a compound of formula Ia-Ic, methods of making such compounds, and methods of using such compounds, e.g., as inhibitors of bacterial RNA polymerase and as antibacterial agents.
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Page/Page column 88
(2014/01/09)
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- Facile preparation of thiophene C2-ethers using the Mitsunobu reaction
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The preparation of thiophene ethers generally requires forcing conditions thus limiting the choice of alkyl substituent. Herein, we report the first successful generally applicable conditions for the selective O-alkylation of 2(5H)-thiophenone.
- Harris, Craig S.,Germain, Hervé,Pasquet, Georges
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experimental part
p. 5946 - 5949
(2009/04/11)
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- Method for preparing alkyl ethers and aryl ethers
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Method for preparing compounds of the formula (III) by reacting compounds of the formula (II) with a) an alcoholate or b) an alcohol R1-OH and a base in the presence of a Cu-containing catalyst and of a ligand, where X1-5 are independently of one another either carbon or nitrogen, or in each case two adjacent X1R1, with i=1?6, linked by a formal double bond together O, S, NRH or Nrl. The ligands preferably employed are acyclic and/or cyclic oligo- and polyglycols, oligo- and polyamides or oligo- and polyamine glycols of the general formula (IV) k is an integer >0 and n is an integer >1; X and Y are independently of one another O, NH or NR1.
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Page/Page column 3-4
(2008/06/13)
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- 2-(substituted-phenyl)amino-imidazoline derivatives
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This invention relates to IP receptor antagonists selected from the group of compounds represented by Formula I: where:R1 is a group represented by formula (A), (B) or (C); and other substituents as defined in the specification, and their pharmaceutically acceptable salts or crystal forms thereof; and pharmaceutical compositions containing them; and methods for their use as therapeutic agents.
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- Synthesis and antitumor activity of duocarmycin derivatives: A-ring pyrrole compounds bearing 5-membered heteroarylacryloyl groups
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A series of A-ring pyrrole compounds of duocarmycin bearing 5-membered heteroarylacryloyl groups (thienylacryloyl and pyrrolylacryloyl) and heteroarylcarbonyl groups were synthesized and evaluated for in vitro anticellular activity against HeLa S3 cells and in vivo antitumor activity against murine sarcoma 180 in mice. Most of the thienylacrylates displayed in vitro anticellular activity equivalent to 4'-methoxycinnamates. Among the 8- O-[(N-methylpiperazinyl)carbonyl] derivatives of methoxy-thienylacrylates, compound 11b, having 4'-methoxy-2'-thienylacryloyl as segment-B (Seg-B), showed remarkably potent antitumor activity and low peripheral blood toxicity in vivo, which were equal to those of 8-O-[(N-methylpiperazinyl)carbonyl] derivatives of 4'-methoxycinnamates, compared with the A-ring pyrrole derivatives having the trimethoxyindole skeleton in SegB. On the other hand, the 2'-pyrrolylacrylates having a double bond as spacer showed 102- to 103- fold stronger anticellular activity than 2'-pyrrolecarboxylates (IC500.3 nM, 72 h-exposure). The 8-O-acetate and 8-O-[(N-methylpiperazinyl)carbonyl] derivatives of 2'-pyrrolylacrylates exhibited an antitumor effect at a lower dose compared with the 8-O-[(N-methylpiperazinyl)carbonyl] derivatives of 4'- methoxycinnamate (1j). Moreover, it was expected that the antitumor activity would be increased by the strength of the extra hydrogen bond formed between the nitrogen of the pyrrole amido group and DNA, owing to the increase of the number of N-methyl-2'-pyrrolecarboxamide units. However, 2'-pyrrolylacrylates having three N-methyl-2'-pyrrolecarboxamide units showed nearly equal antitumor activity to 2'-pyrrolylacrylates having only one N-methyl-2'- pyrrolecarboxamide unit.
- Amishiro, Nobuyoshi,Nagamura, Satoru,Kobayashi, Eiji,Okamoto, Akihiko,Gomi, Katsushige,Saito, Hiromitsu
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p. 1393 - 1403
(2007/10/03)
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- Copper(I) Halide Catalysed Synthesis of Alkyl Aryl and Alkyl Heteroaryl Ethers
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A number of alkyl aryl and alkyl heteroaryl ethers have been prepared from (hetero) aryl halides (mainly bromides) and sodium alkoxides, using copper(I)bromide as a catalyst.The influence of the main solvent, the halogen atom, reaction temperature and the presence of oxygen upon the rate and selectivity has been studied.Furthermore the decomposition of the catalyst and the reduction of the aryl halide are studied.
- Keegstra, Menno A.,Peters, Theo H. A.,Brandsma, Lambert
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p. 3633 - 3652
(2007/10/02)
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- PROTIODESILYLATION OF SUBSTITUTED 2-TRIMETHYLSILYLTHIOPHENS
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First-order rate constats at 50 deg C have been determined for cleavage of the thiophen compounds XC4H2SSiMe3-2 in mixtures of (a) MeOH (5 vol.) with aqueous HClO4 (2 vol.) and (b) CH3CO2H (4 vol.) with aqueous H2SO4 (3 vol.) Relative rates krel, in the first medium are (X =) 5-OMe, 7 200; 5-Me, 36; H, 1.00; 5-Cl, 1.08E-1; 5-Br, 9.0E-2; 3-Br, 5.0E-2; 4-Br, 4.9E-3, and in the second medium 5-Me, 36; H, 1.00; 5-Cl, 1.28E-1; 5-Br, 9.8E-2; 3-Br, 5.5E-2; 4-Br, 6.5E-3; 5-NO2, 9.1E-7; 3-NO2, 7.1E-7.Except for the nitro-compounds, the two sets of log krel values show excellent linear correlations with values for the corresponding XC6H4SiMe3 compounds, with 3-, 4-, and 5-X in the thiophen ring being taken as equivalent to o-, m-, and p-X groups, respectively, in the benzene ring, the effects of substituents being a litle larger in the thiophen than the benzene system; 3- and 5-O2NC4H2SSiMe3 are less reactive than would be expected from the correlations.Again with the exception of the data for the nitro-compound, the krel values for the 4- and 5- substituted thiophens show very good correlation with ?m+ and ?p+ constants.
- Seconi, Giancarlo,Eaborn, Colin
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p. 931 - 934
(2007/10/02)
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- THE RATES OF BASE CLEAVAGE OF SUBSTITUTED 2-THIENYLTRIMETHYLSILANES. AB INITIO CALCULATIONS OF THE ACIDITIES OF MONOSUBSTITUTED THIOPHENS
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Rates of cleavage in NaOMe-MeOH at 50 deg C have been determined for the mono-substituted 2-trimethylsilylthiophens X*C4H2S*SiMe3-2 with X = H, 3-NO2, 3-Br, 4-Br-, and 5-NO2, -CN, -COPh, -Me, -OMe and -NMe2, and for one disubstituted compound, 4,5-Br2*C4HS*SiMe3-2.For several compounds the rate and product isotope effects have also been determined.The energies involved in the process X*C4H3S X*C4H2S- for deprotonation at the 2-position have been calculated by an ab initio method (STO-3G), and the results used in analysis of the substituent effects in the cleavage of the XC4H2S*SiMe3-2 compounds.The results are consistent with the view the aryl anions separate in the rate-determining step of the cleavage.The isotope effects are all close to unity, whereas by comparison with results for XC6H4CH2SiMe3 and related species of similar reactivity, values in the region of 10 would be expected for the 3- and 5-NO2 compounds if the product isotope effect for a carbanion R depended only in the pKa of RH.The difference between the thienyl- and benzyl-type anions is attributed to the absence of conjugative delocalization of the charge in the former. Approximate pKa values are derived for the 2-positions of the X*C4H3S compounds.
- Seconi, Giancarlo,Eaborn, Colin,Stamper, John G.
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p. 153 - 168
(2007/10/02)
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- SYNTHESIS AND TRANSFORMATIONS OF SULFIDES OF THE THIOPHENE SERIES.
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Isomeric alkoxy(alkylthio)formylthiophenes were synthesized from 4-iodo-2-methoxythiophene, and the structures of the products of Vilsmeier formylation of 2-methoxy-5-methythiothiophene were confirmed.
- Gol'dfarb, Ya. L.,Kalik, M. A.,Zav'yalova, V. K.
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p. 126 - 132
(2007/10/02)
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- Sulfonation of aromatic compounds in the presence of solvents
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A process for the sulfonation of aromatic compounds wherein an aromatic substance consisting of one or more aromatic compounds susceptible to the action of sulfur trioxide is formed into a reactant by admixture with one or more organic liquids, substantially inert to sulfur trioxide under the conditions of the process, which reactant is brought to boiling at a temperature not greater than 100° C under a pressure of from 0.1 mm Hg to atmospheric pressure, gaseous sulfur trioxide is introduced thereinto thereby causing it to continue to boil, the component or components of the reactant thus volatilized is or are reconverted to liquid in a heat-exchanger and recycled to the reaction chamber, and the pressure in the reaction chamber and the rate at which the gaseous sulfur trioxide is introduced into the reactant are controlled so as to ensure that there is always present in the reaction chamber an amount of volatilizable matter exceeding that amount volatilizable by the heat of reaction of the aromatic substance present in the reaction chamber with the gaseous sulfur trioxide in contact with said aromatic substance and that the temperature of the reaction mixture is a temperature of 100° C or below.
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